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Hydrodeoxygenation catalyst for biological oil and fat as well as preparation and application of hydrodeoxygenation catalyst

A deoxygenation catalyst, bio-oil technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, preparation of liquid hydrocarbon mixture, etc. Application limitations, poor catalyst stability, etc., to achieve the effects of excellent hydrodeoxygenation capacity, strong hydrodecarboxylation/decarbonylation capacity, and improved stability

Pending Publication Date: 2022-05-24
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Chinese patent CN 101709225 A discloses using sunflower oil as raw material, using 2% Pd / BaSO 4 Catalyst, at 270°C, 3.0MPa, reacted in a reactor for 7 hours, the conversion rate of sunflower oil can reach 100%, and the product is long-chain alkanes, but precious metals are expensive and have limited reserves, so large-scale industrial applications are limited
In a high-pressure fixed-bed reactor, biodiesel can be obtained from castor oil through hydrodeoxygenation. However, metal phosphides are used as catalysts, which are complicated to prepare and are easily deactivated in the presence of water.
Chinese patent CN 101270300 A discloses sulfurized Ni-Mo / TiO modified by F or P 2 -Al 2 o 3 As a biodiesel hydrodeoxygenation catalyst, the catalyst shows good hydrodeoxygenation performance, but sulfur loss occurs during the reaction process, and sulfur reagents need to be continuously replenished to maintain the high stability of the catalyst; in addition, due to the hydrodeoxygenation The product contains sulfur, and subsequent desulfurization treatment is required to increase the production cost
[0005] However, most of the existing non-sulfurized oil hydrodeoxygenation catalysts use alumina as the carrier. Due to the high reaction temperature, a large amount of water is generated during the hydrodeoxygenation process, which leads to poor catalyst stability and is not suitable for large-scale industrialization. Therefore, it is of great practical significance and industrial application value to develop a new type of non-sulfurized oil hydrodeoxygenation catalyst with high activity and high stability

Method used

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  • Hydrodeoxygenation catalyst for biological oil and fat as well as preparation and application of hydrodeoxygenation catalyst
  • Hydrodeoxygenation catalyst for biological oil and fat as well as preparation and application of hydrodeoxygenation catalyst
  • Hydrodeoxygenation catalyst for biological oil and fat as well as preparation and application of hydrodeoxygenation catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1 nickel-molybdenum-lanthanum / nickel-Al 2 O 3

[0031] Weigh an appropriate amount of microsphere γ-Al 2 O 3 The carrier was evacuated at 100°C for 2h, and then lowered to room temperature, denoted as A.

[0032] Weigh 4.96gNi (NO 3 ) 2 ·6H 2O, after adding 20ml of deionized water to fully dissolve, 20g of A was immersed in the solution, dried in the shade, dried at 120°C for 12h, and calcined at 800°C for 6h in a nitrogen atmosphere to obtain B. The sample of Example 1 was subjected to XRD test. , there are diffraction peaks at 2θ=37°, 45.1° and 65.7°, belonging to NiAl 2 O 4 The characteristic peaks of the spinel structure can be seen in the microspheres of γ-Al 2 O 3 There is a nickel-aluminum spinel structure on the surface, and the surface contains Al with a nickel-aluminum spinel structure 2 O 3 Metal Ni accounts for Al in the carrier 2 O 3 The quality fraction of 5%;.

[0033] Weigh 1.56gLa (NO 3 ) 3 ·6H 2 After O was fully dissolved in ...

Embodiment 2

[0035] Example 2 nickel-molybdenum-lanthanum / nickel-Al 2 O 3

[0036] Using the vacuum-treated microsphere γ-Al in Example 1 2 O 3 Carrier, denoted as A.

[0037] Weigh 4.95g Ni (NO 3 ) 2 ·6H 2 O. After adding 20ml of deionized water to fully dissolve, 20g of A was immersed in the solution, dried in the shade, dried at 120°C for 12h, and calcined at 900°C for 6h under a nitrogen atmosphere to obtain B.

[0038] Through the XRD test on the sample of Example 2, diffraction peaks appear at 2θ=37°, 45.1° and 65.7°, which belong to NiAl 2 O 4 The characteristic peaks of the spinel structure can be seen in the microspheres of γ-Al 2 O 3 There is a nickel-aluminum spinel structure on the surface, and the surface contains Al with a nickel-aluminum spinel structure 2 O 3 Metal Ni accounts for Al in the carrier 2 O 3 The quality score of 4.99%.

[0039] Weigh 1.81gLa (NO 3 ) 3 ·6H 2 After O was fully dissolved in 20ml of deionized water, B was immersed in the solution,...

Embodiment 3

[0041] Example 3 Nickel-tungsten-lanthanum / nickel-Al 2 O 3

[0042] Weigh an appropriate amount of strip γ-Al 2 O 3 The carrier was evacuated at 100°C for 2h, and then lowered to room temperature, denoted as A.

[0043] Weigh 1.24gNi (NO 3 ) 2 ·6H 2 O. After adding 20ml of deionized water to fully dissolve, 20g of A was immersed in the solution, dried in the shade, dried at 120°C for 12h, and calcined at 800°C for 6h under nitrogen atmosphere to obtain B.

[0044] Through the XRD test on the sample of Example 3, weak diffraction peaks appear at 2θ=37°, 45.1° and 65.7°, which belong to NiAl 2 O 4 The characteristic peaks of the spinel structure can be seen in the microspheres of γ-Al 2 O 3 There is a nickel-aluminum spinel structure on the surface, and the surface contains Al with a nickel-aluminum spinel structure 2 O 3 Metal Ni accounts for Al in the carrier 2 O 3 The mass fraction of 1.25%.

[0045] Weigh 0.23gLa (NO 3 ) 3 ·6H 2 After O was fully dissolved ...

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Abstract

The invention discloses a catalyst for preparing alkane through catalytic hydrodeoxygenation of biolipid and application of the catalyst, and belongs to the new technical field of biological energy. Comprising the following steps: (1) soaking gamma-Al2O3 in a Ni-containing soluble metal salt solution, and then drying and roasting to generate a nickel aluminate spinel structure on the surface of Al2O3; (2) dipping Al2O3 with a nickel aluminate spinel structure on the surface as a carrier in a soluble metal salt solution of a rare earth element, and then drying and roasting; and (3) dipping soluble metal salt of Ni, Mo or / and W, drying and roasting to obtain the supported metal catalyst. The catalyst is used for carrying out hydrodeoxygenation reaction on a trickle bed reactor by taking biolipid as a raw material, the conversion rate can reach 100%, and the oil product yield can reach 82%. The catalyst provided by the invention has stable surface properties. In addition, the catalyst can replace a sulfurized catalyst for a traditional hydrodeoxygenation reaction, so that the harm of sulfides to the environment is avoided, and the catalyst is suitable for industrial production.

Description

technical field [0001] The invention belongs to the new technology field of biological energy, and in particular relates to a non-sulfided catalyst for catalyzing the hydrodeoxygenation of biological oils and fats to prepare straight-chain alkanes and its application. Background technique [0002] With the increasing consumption of non-renewable resources, the increasing price of fossil energy and the increasingly stringent environmental protection requirements, energy shortages and energy conservation and emission reduction have restricted economic development. [0003] As a kind of abundant and renewable resource, bio-oil is a potential new energy source. The main component of bio-oil is higher fatty acid ester, which has relatively large relative molecular weight and high oxygen content (generally as high as 35% to 60%), so it must be refined by hydrodeoxygenation to reduce the oxygen content and improve its quality before it can be used as a biological oil. Motor fuel a...

Claims

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Application Information

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IPC IPC(8): B01J23/887B01J23/888C10G3/00
CPCB01J23/8871B01J23/888B01J23/8885C10G3/46C10G3/48B01J23/005C10G2400/04Y02P30/20
Inventor 王涛丁云杰卢巍龚磊峰于婷婷
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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